1. Field of the Invention
This invention relates to the synthesis of hydrocarbons from carbon monoxide and water. More particularly, CO and H.sub.2 O are contacted with a water-soluble ruthenium catalyst in an aqueous solvent.
2. Description of the Prior Art
It is known to convert CO and H.sub.2 O into hydrocarbons. These reactions, however, are generally heterogeneous since the catalytic system usually involves transition metals in their elemental state.
W. H. E. Mueller and H. Hammer (Makromol. Chem., 70:1-11 (1964)) describe the heterogeneous synthesis of high molecular weight paraffins from carbon monoxide in aqueous suspension of ruthenium metal. High-melting paraffin waxes (up to 131.degree. C., mole wts. up to 7000) are prepared by feeding CO into an aqueous suspension of finely dispersed metallic ruthenium (75-200 atm., 150.degree.-260.degree. C.). Similarly, German Pat. No. 1,092,458 describes the preparation of hydrocarbons and oxygen-containing compounds by the heterogeneous reaction of carbon monoxide with water in the presence of aqueous catalyst suspensions at 180.degree.-300.degree. C. and greater than 4 atmosphere pressure. Catalysts used are Co, Ni or stabilized Fe compounds in suspension. Best results are obtained using suspension of ruthenium catalysts.
J. Halpern, B. R. James and A. L. W. Kemp (J. Am. Chem. Soc., 83:4097-8 (1961)) report the hydration of acetylenic compounds to aldehydes or ketones using ruthenium (III) chloride in aqueous solution to give a reaction which proceeded under mild and apparently homogeneous conditions.
U.S. Pat. No. 3,055,949 teaches the preparation of hydroquinone and quinhydrone by the reaction of acetylene and carbon monoxide in a liquid reaction medium and in the presence of a catalytic amount of a halide, a carbonyl or the acetylacetonate of ruthenium or rhodium. The solvent used may be a hydroxylic compound, i.e., water or an alcohol, a ketonic compound or an ether. The catalyst and the solvent are charged to the reaction vessel and then a metered amount of acetylene is introduced. Carbon monoxide is then introduced to provide at least one mole CO per mole acetylene. Hydroquinone or quinhydrone are recovered.
German Pat. No. 2,445,193 teaches a process for the preparation of diethylketone which comprises reacting ethylene, CO and H.sub.2 O at 150.degree.-300.degree. C. and 100-350 atm pressure in the presence of an inert solvent such as benzene, toluene, xylene, chlorobenzene, etc., using a Ru halide (hydrate) as catalyst.
It is also known to prepare high molecular weight hydrocarbons from carbon monoxide and hydrogen. U.S. Pat. No. 2,632,014 discloses that high molecular weight polymethylenes can be prepared from the reaction of CO and H.sub.2 in the presence of water and a ruthenium catalyst such as ruthenium dioxide, ruthenium metal, ruthenium carbonyls and the ruthenium salts of organic carboxylic acids. The molecular weight of the product can be controlled by adjusting the pH and CO:H.sub.2 ratio. Hydrogen is not a reactant in the instant invention.
It is an object of this invention to provide a process based on a homogeneous catalytic system for converting a CO and H.sub.2 O into hydrocarbons. It is a further object to prepare deuterated or tritiated long-chain hydrocarbons.